Deketo-benzo-dipyrole polymers

ABSTRACT

ROLE-3,7-DIONE AND THE POLYMERS PREPARED THEREFROM BY OXIDATIVE POLYMERIZATION OF THE INDIVIDUAL MONOMERS OR MIXTURES OF THE TWO MONOMERS. THE MONOMERS ARE USEFUL AS INSECTICIDES AND BIOCIDES, AND THE POLYMERS ARE USEFUL AS DYES AND SEMICONDUCTORS.   THE COMPOUNDS ARE:   DIONE, 1,2,3,5,6,7-HEXAHYDROBENZO(1,2-B:4,5-B&#39;&#39;)DIPYR-   1,2,3,5,6,7-HEXAHYDROBENZO(1,2-B:5,4-B&#39;&#39;)DIPYRROLE-3,5-

,fiWAM Patented Aug. 117, 1971i I o o 0 3,600,401 I g II IIDIKETO-BENZO-DIPYROLE POLYMERS Charles L. Thomas, Swarthmore, Pa.,assignor to Sun Oil Company, Philadelphia, Pa. 5 0 0 HN NE N0 Drawing.Original application Dec. 29, 1966, Ser. No. 605,574, now Patent No.3,505,353. Divided and this 0 C C 0 application Nov. 19, 1968, Ser. No.796,254 l II H Q Int. Cl. C07d 27/40 US. Cl. 260326.11 5 Claims 10 lNaOCl ABSTRACT OF THE DISCLOSURE The compounds are: H

H2N NH3 H 0 0 C NH3 0 HOOC- -OOOH H2N COOH H H a H CICH GOOH CICH COOH11,0 on, E 0 GHQ 2 2 HOOCCHQHN- NHCHZCOOH I] H H II I 0 0 0 H 0 0 o o 0OH 2, 6-dihydro-3,fi-diketobenzo 2, 6-dihydro-3, 7-diket0- (1,2-b:5,4-b)dipyrrole and benz0(1,2-b:4, 5-10) 0 dipyrrole III HOOC -NHOH2COOH andthe polymers prepared therefrom by oxidative polym- HOOCCHZHN C 0 0Herization of the individual monomers or mixtures of the two monomers.The monomers are useful as insecticides l and biocides, and the polymersare useful as dyes and semiconductors. IV E g h H C N 1120/ Tlhis is adivision of application Ser. No. 605,574, filed 20 CH, Dec. 29, 1966,now US. Pat. No. 3,505,353.

0 SUMMARY OF THE INVENTION 0 0 H II The present invention relates tonovel compounds. Par- 2, 6-dihydr0-3, 5-di kcto- 2, 6-dihydr0-3,7-diketm ticularly it relates to novel monomers having the structure g gggg-bzarb) giegggi 31 :4, 5-b

IA (13H, (3H (I311, H 11 N N 49 HNO; 2 N02 H3C\ /OH3 -CH3 "CH3 CH3 l (J(5 50 NO; N02 0 o NaOH or TIA H O O C C O OH 4; E HQN --Nn,

n o on The product for step HA is then carried through steps N C III andIV as shown above. The monomers of the inven- H 9 tion are solid. Theprincipal utility of the monomers is in the polymerization thereof. Themonomers are also useful as insecticides and biocides. The polymers ofthe present invention are useful as vat and the P y Producedthefefromdyes and as organic semiconductors. Polymers suitable for useas vat dyes have a number average molecular DESCRIPTION OF THE INVENTIONweight in the range of 372 to 556, i.e., 2 to 3 repeating The monomersof the present invention may be derived monomer units. The polymersgenerally suitable for use in a number of chemical syntheses, forexample, as shown 0 as semiconductors have a number average molecularschematically below for pyromellitic dianhydride and weight in the rangeof 550 to 5500 wherein there are meta-xylene as starting material. about3 to 30 repeating units.

The polymers of the present invention comprise repeating units selectedfrom the group consisting of and mixtures thereof.

The polymers are prepared from a single pure monomer or a mixture ofmonomers by dissolving in alkaline hydrosulfite and oxidizing withoxygen or air. Alternatively, the monomer is oxidized by permanganate ordichromate. The molecular weight of the polymers is controlled by thedegree of oxidation, i.e., the molecular weight increases withoxidation.

The vat dye polymers are easily used. The polymer is made soluble inwater by treating with an aqueous solution of a reducing agent such assodium hydrosulfite (Na S O and alkali, i.e., NaOH or KOH. In this formthe dye can be impregnated into a textile, paper, leather or the likeand upon exposure to air will be reoxidized by atmospheric oxygen to thestable polymer form. The vat dyes are dark blue through black, theintensity depending on the extent of polymerization.

Once on the material to be dyed, the polymers exhibit unusual stabilityto light, heat, water and organic solvents.

The electrical properties of the high molecular weight polymers such asresistance, conductivity, dielectric constant and the like wouldindicate that they would be excellent semiconductors.

In order to more clearly illustrate the invention the followingnonlimiting examples are submitted. Unless otherwise indicated, partsand percentages are by weight.

Example I Seventy-five grams of pyromellitic dianhydride and 120 g.solid ammonium carbonate are mixed, put in a round bottom flask which isplaced in an oil bath, heated to 225 C. H 0 and CO are evolved. Thereaction is completed when H O is no longer evolved. The residue iscrude pyromellitic diimide.

Forty-five grams of crude diimide and 60 g. NaOH are dissolved in 400cc. of H 0. The solution is cooled and 600 g. of cold 5% sodiumhypochlorite solution added with stirring. The reaction is completed bywarming to 80 C. for 30 minutes. The solution is cooled, neutralizedwith hydrochloric acid and then acidified with acetic acid to liberatethe diamino-diacids, which are separated by filtration.

Two hundred grams of the diamino-diacids, 235 g. of sodium chloroacetateand 300 cc. of water are mixed and neutralized with NaOH. The mixture isheated under reflux for four hours. On cooling, hydrochloric acid isadded to neutralize. Acetic acid is added to liberate the diacids whichare then separated by filtration.

Fifteen parts of the diacids are added to a solution of 25 parts of NaOHin parts of Water. The mixture is heated while stirring (110 C. maximum)to dryness and the cake finely powdered. Fifteen parts of paraffin(melting point about 0 C.) and the powdered solid are heated in an ironpan with stirring to 250-270 C. Steam is evolved and the mass foams.When reaction ceases (260- 280 C.) the mixture is cooled, boiled withwater in the absence of air and the liquid filtered from the solidparaffin again in the absence of air. The monomers are liberated byacidifying the liquid and recovered by filtration as a yellowishcrystalline material.

Where the compound is to be used as a dye, instead of liberating themonomers with acid, the aqueous solution can be oxidized with air whereupon the dye stuif separates as a finely divided sludge which isconcentrated into a paste by centrifuging.

i0 and 4 Example II A mixture of 2,4- and2,6-dinitro-1,3-dimethylbenzene, which is prepared by the nitration ofmeta-xylene with HNO is separated, e.g., by crystallizing from alcoholand the 4,6- recovered as crystals. 200 g. of 4,6-dinitro-1,3-dimethylbenzene plus 240 g. of NaOH are dissolved in alcohol andrefluxed five hours. The solution is then saturated with NH and H 5 andrefluxed three hours. The alcohol and excess ammonium sulfide areremoved by heating. The solid is dissolved in water, filtered andneutralized with hydrochloric acid. The diamino-diacids are liberated byacetic acid and recovered by filtration. The process is continued as inExample I using the diamino-diacids.

, Example III Five parts of the dyestutf paste prepared in Example Icontaining about 20% dyestufi are mixed with 3 parts of hot water. Tothis is added 17 parts of caustic soda solution (sp. gr. 1.38) and themixture heated to 50 C. Twenty-five parts of sodium hydrosulfitesolution (sp, gr. 1.1) are added and the temperature kept at 50 C. toreduce the dyestuff to the leuco form and disperse it in the solution.

The solution is diluted with 300 parts of warm water. Cotton fibers arethoroughly soaked therein. The fibers are wrung out and dried. Duringhandling and drying in the air, the color develops.

As a polymer, the 20% dyestuif paste may be dried and the powder useddirectly as a molding powder, fabricating articles by heat and pressureThe invention claimed is:

1. A polymer consisting of repeating units selected from the groupconsisting of H :C/ C: N o H II Y 0 wherein the polymer has a molecularweight in the range of 372 to 5500.

2. A composition according to claim 1 wherein the molecular weight is inthe range of 372 to 556.

3. A polymer according to claim 1 wherein the unit is II o 4. A polymeraccording to claim 1 wherein the unit is 5. A polymer according to claim1 wherein the unit is a mixture of

